Compositions based on iodopropynyl-and formaldehyde donor compounds and to their use as preservatives

ABSTRACT

Compositions having broad effectiveness against bacterial and fungi, which comprise (a) an iodopropynylbutyl compound and (b) one or more formaldehyde donor compounds, the formaldehyde donor compounds being N-formals, O-formals and/or a combination thereof. The compositions are also stable and effective in the form of liquid concentrates. The present invention also relates to the use of such compositions in industrial products and to industrial products which comprise these compositions.

CROSS REFERENCE TO RELATED APPLICATION

[0001] This application is a divisional application of application Ser.No. 09/424,447 filed on Nov. 23, 1999, which is the 35 USC 371 nationalstage of International Application PCT/IB98/00766 filed on May 19, 1998.

FIELD OF THE INVENTION

[0002] The present invention relates to compositions or preservativesfor use in industrial products, which protect these products againstbacterial and fungal infestation over extended service lives.

BACKGROUND OF THE INVENTION

[0003] Preservatives having a biocidal action for use in industrialproducts such as cutting fluids, cutting fluids which have been mixedwith water, industrial emulsions or other water-based industrialproducts, and also for household products, such as, for example,cleaning products or cosmetics, such as, for example, bodycare products,are when required generally added to the products to be preserved in lowconcentration in the form of concentrates.

[0004] They protect these products against infestation by bacteria,fungi and yeasts and contribute to long service lives of industrialproducts, such as, for example, cutting fluids which have been mixedwith water, and to a long useful life of household products and cosmeticproducts.

[0005] During their manufacture, storage and their use, preservativesare subject to certain requirements which arise inter alia from the wayin which they are added to the abovementioned products in the form ofliquid concentrates.

[0006] A known fungicidal active ingredient which is frequently usedtoday is iodopropynylbutyl carbamate (IPBC), which is marketed, forexample, by Troy Chemie as an organic fungicide preparation in the formof a 20% strength solution of the active ingredient in glycols under thetrade name Troyshield F20.

[0007] In order to achieve a likewise satisfactory bactericidal effect,it is, however, necessary to combine IPBC with other active substances,e.g. formaldehyde donor compounds. Regarding compatibility with IPBC,however, there are problems when used in concentrates containingformaldehyde donor compounds in the form of strongly alkalinebactericides. Thus, for example, Troy Chemie's technical instructionsheet for Troyshield F20™ advises against mixing it with stronglyalkaline bactericides, such as, for example,1,3,5-tris(hydroxyethyl)hexahydrotriazine (Grotan BK™), because thestability of fungicidally and bactericidally active preparations basedon IPBC is impaired.

[0008] There has thus been a search for potential ways of improving thestability of IPBC-based compositions for use as preservatives having afungicidal and bactericidal action.

[0009] The prior art includes, for example, an almost white powderconsisting of IPBC and a mixture of1,3-bis(hydroxymethyl)-5,5-dimethylhydantoin andhydroxymethyl-5,5-dimethylhydantoin GlydantPlus™, Lonza AG), which isused as a preservative for cosmetic preparations.

[0010] U.S. Pat. No. 5,496,842 and U.S. Pat. No. 5,428,050 disclosewater-soluble compositions comprising a combination of iodopropynylbutylcompounds and N-methylol compounds. It is disclosed that compositionscomprising IPBC and N-methylol compounds in a weight ratio of from 1:100to 1:2000 are in the form of a concentrate powder which, as awater-soluble additive, can be added to industrial products, inparticular bodycare products, which then include from 0.01% to 2% ofthese compositions. The N-methylol compounds mentioned in U.S. Pat. No.5,496,842 and U.S. Pat. No. 5,428,050 do, however, include compoundswhich are not compatible with IPBC, for example1,3,5-tris(hydroxyethyl)-hexahydrotriazine.

[0011] EP 0327220 B1 discloses a combination of an iodopropynyl compoundwith known formaldehyde donors. The disclosed compositions include, aspreferred iodopropynyl compound, IPBC and, as formaldehyde donors,non-toxic and odorless compounds which are suitable for use in bodycareproducts, for example urea derivatives and dimethyloldimethylhydantoin.The compositions of EP 0327200 B1 are likewise added, for example, inthe form of solid, water-soluble mixtures, to the products to bepreserved.

[0012] The known pulverulent concentrates do, however, have a number oftechnical disadvantages, such as, for example, a tendency towardclumping, a relatively low dissolution rate, a tendency to form dust andthe like.

[0013] Moreover, the use of odourless, i.e. usually nonvolatile,formaldehyde donors does not, in the case of certain applications, offeradequate antimicrobial protection in the gaseous phase, since no vapourphase of volatile, formaldehyde compounds is present.

[0014] In addition, the N-methylols in the form of liquid concentratesmentioned in U.S. Pat. No. 5,496,842 and U.S. Pat. No. 5,428,050 are notcompatible with IPBC, i.e. are unstable and are thus also insufficientlystable in liquid products, such as cutting fluids, which are to bepreserved. This is therefore a disadvantage particularly because inindustrial products such as cutting fluid emulsions, desired pHstabilization and buffering is achieved inter alia by adding basic,tertiary amines.

SUMMARY OF THE INVENTION

[0015] The object of the present invention is to provide compositionswhich protect industrial products against bacterial attack and fungalinfestation over extended service lives. The novel compositions shouldthemselves be sufficiently stable and should not decompose under variousconditions. In addition, they should be easy to handle and haveadvantageous technical properties and be easily incorporated intoindustrial products.

[0016] Another object of the present invention is to provide biocidalcompositions which include iodopropynylbutyl compounds and formaldehydedonor compounds which are compatible therewith. It should be possible tometer these compositions into standard commercial industrial products,for example by adding a liquid preparation.

[0017] Another aim of the present invention is to provide compositionswhich have improved vapour phase effectiveness compared with the priorart and are sufficiently stable over a wide pH range.

[0018] A further object of the present invention is to provideindustrial products, such as, for example, cutting fluids, which aredistinguished from the prior art by increased stability and improvedeffectiveness.

[0019] This object is achieved by a composition which includes (a) aniodopropynylbutyl compound selected from iodopropynylbutyl esters,ethers, acetals, carbamates and carbonates and (b) one or moreformaldehyde donor compounds, and is characterized in that theformaldehyde donor compounds are N-formals formed by the reaction orcondensation of a monovalent or polyvalent, amino-substitutedC₁-C₁₀-alkyl, -aryl or -aralkyl alcohol and a formaldehyde-supplyingcompound, and/or O-formals formed by the reaction of a monovalent orpolyvalent C₁-C₁₀-alkyl, -aryl -aralkyl alcohol or of a glycol or glycolether and a formaldehyde-supplying compound, and/or a combinationthereof.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The novel preparations preferably comprise iodopropynylbutylcarbamate (IPBC), and the formaldehyde donor compound is preferably anN-formal selected from 3,3′-methylenebis(5-methyloxazolidine) (Mar 71™),3,3′-methylenebis(tetrahydro-2H-1,3-oxazine) and1-aza-5-ethyl-3,7-dioxabicyclo-(3,3,0)octane, particularly preferably acombination of 3,3′-methylenebis(5-methyloxazolidine) (Mar 71™) andIPBC.

[0021] The compositions comprising the novel iodopropynylbutyl compoundand N-formals include the components in amounts, based on thecomposition, of from 0.1 to 20% by weight of iodopropynylbutyl compoundand from 99.9 to 80% by weight of N-formal, preferably from 1 to 10% byweight of iodopropynylbutyl compound and from 99 to 90% by weight ofN-formal. The composition particularly preferably comprises from 4 to 6%by weight of iodopropynylbutyl compound, in particular iodopropynylbutylcarbamate, and from 96 to 94% by weight of N-formal, in particular3,3′-methylenebis(5-methyloxazolidine).

[0022] In addition or alternatively to the N-formals according to theinvention, the novel compositions may also comprise O-formals formed bythe reaction or condensation of formaldehyde-supplying compounds andmono- or polyvalent C₁-C₁₀-alkyl, -aryl or -alkaryl alcohols or glycolsor glycol ethers, such as, for example, 1,2-propylene glycol hemiformal,ethylene glycol mono- and/or bisformal, butyldiglycol hemiformal,butylglycol hemiformal, benzyl glycol hemiformal, dipropylene glycolhemiformal and the like.

[0023] The compositions comprising the iodopropynylbutyl compoundaccording to the invention and O-formals include the components inamounts, based on the composition, of from 0.1 to 20% by weight ofiodopropynylbutyl compound and from 99.9 to 80% by weight of O-formal,preferably from 1 to 10% by weight of iodopropynylbutyl compound andfrom 99 to 90% by weight of O-formal. The composition particularlypreferably comprises from 4 to 6% by weight of iodopropynylbutylcompound, in particular iodopropynylbutyl carbamate and from 96 to 94%by weight of O-formal, in particular from 96 to 94% by weight of1,2-propylene glycol hemiformal.

[0024] Particularly suitable compositions are also those which comprisefrom 0.1 to 20% by weight, of an iodopropynylbutyl compound and from99.9 to 80% by weight of a mixture of N- and O-formals, the weight ratioof N- to O-formals being from 10:1 to 1:10, preferably from 9:1 to 8:2and particularly preferably from 2:1 to 1:2. These compositionspreferably comprise from 1 to 10% by weight of iodopropynylbutylcompound and from 99 to 90% by weight of the mixture of N- andO-formals. Such a composition particularly preferably comprises from 4to 6% by weight of iodopropynylbutyl compound, in particulariodopropynylbutyl carbamate, and from 96 to 94% by weight of the mixtureof N- and O-formals, in particular from 96 to 94% by weight of a mixtureof 3,3′-methylenebis(5-methyloxazolidine) and 1,2-propylene glycolhemiformal.

[0025] The novel compositions are preferably in stable liquid, viscousliquid or paste form, so that they are easy to handle and can be addedeasily to an industrial product at any time in order to preserve it.

[0026] In addition to the biocidally effective components, the novelcompositions may comprise further additives and/or auxiliaries, such asemission-reducing additives, viscosity-modifying additives, wettingagents and solvents which have a favourable effect on the technicalproperties of the compositions, such as, for example, solubility inwater, in total amounts of less than 90% by weight, preferably of lessthan 30% by weight and particularly preferably of less than 15% byweight. Here, the mixing ratios of the individual additives to oneanother are in the customary ranges known for biocidal compositions.

[0027] Particularly suitable compositions are those which comprise asolvent which is selected from 1,2-propylene glycol,1-methoxy-2-propanol, phenoxypropanol and phenoxyethanol.

[0028] For example, the addition of certain glycols, preferably1,2-propylene glycol, in amounts of from 1 to 20% by weight, based onthe composition, has a positive influence on the odour of thecompositions and reduces the emission of readily volatile substances,such as, for example, formaldehyde.

[0029] Particularly suitable compositions are those which, based on thecomposition, include the following components:

[0030] a) from 0.1 to 20% by weight, preferably from 1 to 10% by weightand particularly preferably from 4 to 6% by weight, of an iodopropynylcompound according to the invention and

[0031] b) from 99.8 to 80% by weight, preferably from 99 to 90% byweight and particularly preferably from 96 to 94% by weight, of amixture of solvents and N-formals according to the invention or of amixture of solvents and O-formals according to the invention or of amixture of a combination of N- and O-formals and solvents and also otheradditives as described above, the weight ratio of formal to a solventbeing from 50:1 to 1:10 and preferably greater than 9:1.

[0032] As well as the described additives and solvents, which contributeto improving the properties of the novel compositions, the latter maycomprise further known biocidal active ingredients, such as, forexample, isothiazolones or mercaptopyridines, of whichN-octylisothiazolone (Kathon 893™) and 2-mercaptopyridine N-oxide, inparticular in the form of its 40% strength aqueous sodium salt solution(Pyrion-Na™), are particularly preferred;

[0033] The composition may also comprise further additives which improveits stability.

[0034] In a specific embodiment of the present invention, thecomposition, as described above? comprises between 1% and 10% by weightof IPBC, between 85% and 98,5% by weight of 3-3′-methylene bis(5-methyloxazolidine) and between 0,5% and 5% by weight of a stabilizerselected from triethanolamine, pyriondisulfide, sodium sulfate oraluminium oxide.

[0035] The novel compositions are in the form of a stable liquidconcentrate, a stable working solution prepared by diluting theconcentrate, a stable emulsion or a stable suspension. The compositioncan thus be metered easily and also has a good shelf life and does notdecompose under practical conditions. The good handling properties ofthe composition, compared with the storage, preparation and metering inof active ingredients present in two-component systems, areadvantageous.

[0036] In particular, the novel composition is in the form of aconcentrate, in which case the following requirements placed onconcentrates are satisfied:

[0037] broad effectiveness (e.g. against bacteria, yeasts and fungi)

[0038] storage stability, transportation stability and thermal stability

[0039] relative insensitivity towards heat and light

[0040] compatibility with packing materials

[0041] adequate solubility in water and homogeneous distributionproperties to achieve problem-free incorporation in the products to bepreserved (e.g. aqueous solutions or hydrous products)

[0042] good incorporation into anhydrous or low-water products

[0043] vapour phase effectiveness

[0044] adequate pH compatibility, in particular up to pH 11

[0045] sufficiently low viscosity to enable simple metering.

[0046] The novel compositions may effectively be added to industrialproducts containing industrial preservatives, in particular containerpreservatives, fuel additives, cutting fluid preservatives,preservatives for cutting fluids which have been mixed with water,emulsions and dispersions in the coatings industry or in metalworking,household products, cosmetics and the like, so that the stabilitythereof and the service life of the finished products is increasedcompared with known systems. Increased stability of the novelcompositions is particularly apparent from the lower tendency of theactive ingredient to decompose, less discoloration and reduced formationof undefined decomposition products.

[0047] In addition to the customary constituents, the abovementionedindustrial products thus comprise a novel composition whose componentsare sufficiently compatible both in the concentrate and also in theemulsion or suspension. The industrial products preferably comprise from1 to 10% by weight, preferably from 2 to 5% by weight and in particular2% by weight, of the novel composition.

[0048] Surprisingly, it has been found that the novel combinations ofiodopropynylbutyl compounds and N- and/or O-formals, in particular thecombination of iodopropynylbutyl carbamate (IPBC) and3,3′-methylenebis(5-methyloxazolidine) (Mar 71™), have a stability whichis significantly improved over the prior art, even if they are presentin the form of liquid compositions, such as, for example, solutions oremulsions, in particular liquid concentrates, and are added to theabovementioned industrial products in such a form.

[0049] In addition, the effectiveness of the compositions is improved bythe addition of further additives as in Patent claims 15 to 23, and, inparticular, it is also possible to improve the effectiveness in thevapour phase.

[0050] Moreover, the novel compositions are adequately stable oversufficiently broad pH ranges which are relevant when the compositionsare used in industrial products. Their stability is adequate in the pHrange up to 12, in particular in the range up to pH 11, especially up topH 9.

[0051] The improvements achieved in the compositions as regardsstability, effectiveness and other technically relevant properties, suchas pH stability and emission behaviour, are illustrated by the examplesbelow.

EXAMPLES

[0052] The following abbreviations are used in the examples below:

[0053] IPBC=iodopropynylbutyl carbamate

[0054] Mar 71™=3,3′-methylenebis(5-methyloxazolidine)

[0055] Grotan BK™=1,3,5-tris(hydroxyethyl)hexahydrotriazine

[0056] BDG=butyldiglycol

[0057] POE=phenoxyethanol

[0058] DPG=dipropylene glycol

[0059] PM=1-methoxy-2-propanol

[0060] PP=phenoxypropanol

[0061] Kathon 893™=45% strength N-octylisothiazolone solution in1,2-propylene glycol

[0062] PE=polyethylene

[0063] PLG=propyleneglycol

[0064] Preventol D2™=benzyl alcohol hemiformal

Example 1

[0065] Compositions of IPBC and Mar 71™ with and without 1,2-propyleneglycol as solvent

[0066] In a test series, compositions based on (90-x)% by weight of Mar71+x% by weight of IPBC+10% by weight of 1,2-PLG were prepared. TheIPBC-containing mixtures were slightly cloudy and had to be filtered togive clear, colourless to pale yellow solutions, which were stored at atemperature of +40° C. in clear glass in order to test the stability ofthe compositions.

[0067] Table I shows the development, determined by means of HPLC, ofthe IPBC concentration of the solutions with time over a period of 3months. Investigations were carried out on solutions having an IPBCstarting content of from 0 to 10% by weight. TABLE I IPBC contents: [%by wt.] 1 3 5 10 After 1 month at + 40° C. 0.76 2.35 3.83 7.40 After 2months at + 40° C. — 0.62 1.88 3.04 5.66 After 3 months at + 40° C. 00.52 1.53 2.49 4.50 —

[0068] In a second test series, compositions based on (100-x)% by weightof Mar 71™+x% by weight of IPBC without the addition of 1,2-PLG wereprepared. The IPBC-containing mixtures were likewise slightly cloudy andwere therefore filtered to obtain colourless to pale yellow solutions.These solutions were stored in clear glass at a temperature of +40° C.over three months. The development with time of the IPBC contents,determined by means of HPLC, is given in Table II for IPBC startingcontents of from 0 to 10% by weight. The stability of the compositionsin the absence of 1,2-PLG is negligibly greater, although in both casesthe stability of the compositions is adequate over a sufficiently longstorage period.

[0069] Furthermore, the formaldehyde emission was measured using aDräger tube after storage for about three months at a temperature of+40° C. The formaldehyde emission was determined using Dräger tubes 6733 081 in accordance with Dräger instructions for use no. 234-33081(Drägerwerk AG, Germany), which involved in each case carrying out 10strokes at 21° C. over a 50 ml wide-necked glass containing 5 g of thesample to be investigated. It was found that the formaldehyde emissionincreases with increasing IPBC content, as the results in the last lineof Table II show. The biocidal effectiveness of the compositions in thegas phase thus also increases with increasing IPBC content in anadvantageous manner.

Example 2

[0070] Compositions of IPBC and various N-formals

[0071] The stability and compatibility of IPBC in compositionscontaining 3% by weight of IPBC, from 80 to 97% by weight of N-formalsand 17% by weight of 1,2-PLG were determined as a function of thestorage time after the solutions had been stored at a temperature of+40° C. in clear glass. A summary of the various percentages in thecompositions is given in Table III.

[0072] The initially clear, colourless to slightly yellowish solutionsbecame discoloured to varying degrees after storage for three months ata temperature of +40° C. Only the compositions based on IPBC and Mar 71retained their clear, slightly yellowish appearance.

[0073] In all samples, the odour was characteristic, in some cases beingpungent from the formaldehyde, and in others being amine-like.Composition F had a considerably weaker odour than composition E, whichhad a characteristic pungent formaldehyde odour. TABLE III Compositionin % by wt. A B C D E F G H Grotan BK ™ 97 80 Isopropanolamine-Grotan BKwith 97 80 amine-excess Mar 71 ™ 97 80 Mar 71 ™ variant with amine 97 80excess, not dewatered IPBC  3  3  3  3  3  3  3  3 1,2-PLG — 17 — 17 —17 — 17 Colour after 3 months at +40° C. A and B; clear red-brown C andD: clear, red E and F: clear, yellowish G and H: clear, red

[0074] A summary of the development of the IPBC content, determined bymeans of HPLC (IPBC starting content 3% by weight) in the compositionsinvestigated as a function of the storage period, is given in Table IV.TABLE IV IPBC Contents [% by wt.] A B C D E F G H After 1 <0.03 0.03<0.03 <0.03 2.44 2.27 0.73 0.94 month After 2 <0.03 2.04 1.78 0.53 0.72months After 3,5 1.61 1.34 <0.01 0.04 months

[0075] It is found that IPBC is compatible with different N-formals tovarying degrees. Incompatibility is apparent in particular from arelatively high degree of discoloration following storage and arelatively high degree of IPBC degradation. Thus, for example, thelow-odour Grotan BK TM is incompatible with IPBC. In contrast,preparations based on IPBC and Mar 71 TM with or without 1,2-PLG aresignificantly more stable and, after storage for three months at +40° C.display on IPBC degradation of only about 50%. The formaldehyde emissionincreases with increasing IPBC content. The addition of 1,2-PLG tocompositions which comprise Mar 71 and IPBC is therefore unfavourablefor the stability, but has an advantageous effect on the odour of thecompositions.

Example 3

[0076] Stability of IPBC and Mar 71 in various solvents

[0077] The dependence of the IPBC stability in compositions of IPBC andMar 71™ on various solvents used was tested by storing the compositionsin clear glass at a temperature of +40° C. Investigations were carriedout on preparations containing 1 or 3% by weight of IPBC combined with89 or 87% by weight of Mar 71™ respectively and in each case 10% byweight of a solvent. The results are given in Tables V and VI. TABLE V AC E G I K Composition [% by wt.] Mar 71 89 89 89 89 89 89 IPBC 1 1 1 1 11 1,2-PLG 10 — — — — — DPG — 10 — — — — BDG — — 10 — — — PM — — — 10 — —POE — — — — 10 — PP — — — — — 10 IPBC Content [% by wt.] After 1 monthat + 40° C. 0.74 0.75 0.74 0.77 0.76 0.75 After 2 months at + 40° C.0.63 0.66 0.61 0.62 0.57 0.68 After 3 months at + 40° C. 0.56 0.57 0.540.60 0.60 0.60 Formaldehyde 4 5 3 2 5 5 emission* (in ppm)

[0078] TABLE VI B D F H J L Composition [% by wt.] Mar 71 87 87 87 87 8787 IPBC 3 3 3 3 3 3 1,2-PLG 10 — — — — DPG — 10 — — — BDG — — 10 — — PM— — — 10 — POE — — — — 10 — PP — — — — — 10 IPBC Content [% by wt.]After 1 month at + 40° C. 2.12 2.20 2.15 2.21 2.21 2.17 After 2 monthsat + 40° C. 1.72 1.75 1.89 1.90 1.84 1.77 After 3 months at + 40° C.1.50 1.57 1.47 1.57 1.52 1.57 Formaldehyde emission* (in 5 6 6-7 4 6 8ppm)

[0079] It has been found that the IPBC content of the preparations,determined by means of HPLC, continually decreases throughout thestorage time. The effect of the solvent on the IPBC stability in thepresence of Mar 71 is not very great. All investigated compositionsshowed an IPBC degradation of about 50% after storage for 3 months inclear glass at +40° C. In both test series, the greatest IPBCdegradation was in butyldiglycol (BDG). In contrast, relatively suitablesolvents for the novel compositions are: dipropylene glycol (DPG),1-methoxy-2-propanol (PM), phenoxypropanols (PP) and phenoxyethanol.

[0080] There were clear differences in the formaldehyde emissiondetermination. As Tables V and VI show, a composition containing1-methoxy-2-propanol performs particularly well. For example, comparedwith all the other solvents, the formaldehyde emission was reduced by upto about 50% after three months through the addition of1-methoxy-2-propanol.

Example 4

[0081] Stability of IPBC with various formals

[0082] The stability of various IPBC compositions was tested in clearglass at temperatures of +25° C. and +40° C. Investigations were carriedout with preparations containing 10% by weight of IPBC and 90% offormals. The results are given in Tables VII and VIII. TABLE VIIComposition [% by wt.] M N O IPBC 10 10 10 Mar 71 ™ 90 — — PreventolD2 ™ — 90 — PLG hemiformal — — 90

[0083] TABLE VIII IPBC loss of weight [% wt.] after 5 weeks after 5.5weeks after 6.5 weeks after 3 months composition at 25° C. at 40° C. at25° C. at 40° C. at 25° C. at 40° C. at 25° C. at 40° C. M — — — — 1.4919.13 — — N 6.4 31.1 — — — — — — O — — 26.25 64.90 — — 58.33 69.79

Example 5

[0084] Stability of IPBC compositions containing further additives

[0085] Various additives were added to the compositions M and N and thestability of the resulting preparations were investigated as hereabovementioned in example 7; the results are given in tables IX and X. TABLEIX Composition [% by wt.] M1 M2 M3 M4 N1 IPBC 10 10 10 10 10 Mar 71 ™ 8888 88 88 — Preventol D2 ™ — — — — 88 Triethanolamine  2 — — —  2Pyriondisulfide ™ —  2 — — — Anhydrous sodium sulfate — —  2 — —Aluminium oxide 90 ™ (Merck) — — —  2 —

[0086] TABLE X IPBC loss of weight [% wt.] after 5 weeks after 6,5 weeksComposition at 25° C. at 40° C. at 25° C. at 40° C. M — —  1,49 19,13 M1— — 3,93 22,85 M2 — — 0,0  15,84 M3 — — 3,83 22,0  M4 — — 1,93 13,79 N6,4 31,1 — — N1 2,5 15,8 — —

Example 6

[0087] Odour modification of Mar 71™ by the addition of O-formals

[0088] Compositions containing Mar 71™ with and without 1, 2, 5 and 10%by weight of 1,2-propylene glycol hemiformal were stored at roomtemperature in clear glass. The preparations proved to be sufficientlystable. However, over time a very slightly cloudy sediment formed in themixtures. The addition of 1,2-propylene glycol hemiformal resulted in aclear positive odour modification of Mar 71™.

Example 7

[0089] Compositions based on Mar 71™ containing other biocides

[0090] The stability of compositions which, in addition to 83-x% byweight of Mar 71™, comprise as further biocide 17% by weight ofN-octalisothiazolone (i.e. a 45% strength N-octylisothiazolone solutionin 1,2-PLG=Kathon 893), was tested by storage in clear glass at roomtemperature. As well as Mar 71™ and Kathon 893™, the formulations insome instances comprised 1, 2, 5 and 10% by weight of 1,2-propyleneglycol hemiformal. The preparations were found to be stable. In contrastto the compositions without Kathon 893™, no cloudy sediment formed here.The addition of 1,2-propylene glycol hemiformal resulted in a clearpositive odour modification of Mar 71™.

Example 8

[0091] Stability of compositions containing IPBC and various N-formals

[0092] The stability of a composition containing 3% by weight of IPBC,80% by weight of Mar 71™ and 17% by weight of 1,2-PLG was determined bystorage in polyethylene at room temperature and at +40° C. Thecomposition stored at room temperature was unchanged, i.e. clear andcolourless, after 14 months. The IPBC contents of the investigatedcompositions, determined by means of HPLC, are given in Table VII. Thetest proves that the combination of Mar 71™+IPBC+1,2-PLG is sufficientlystable at various temperatures. TABLE XI RT +40° C. IPBC content [% bywt] after 1 2.63 2.32 month IPBC content [% by wt] after 3 2.59 1.28months IPBC content [% by wt] after 8 2.22 0.59 months

[0093] As well as Mar 71™, the compatibility of IPBC with3,3′-methylenebis(tetrahydro-2H-1,3-oxazine) as a further N-formal wasinvestigated. In addition to IPBC (3% by weight) and the correspondingN-formal (80% by weight), both compositions also additionally comprise17% by weight of 1,2-propylene glycol. The IPBC content was determinedafter storage at room temperature after 1, 3 and 11 months. It has beenfound that a combination of IPBC and3,3-methylenebis(tetrahydro-2H-1,3-oxazine) is also sufficiently stable.As Table VIII shows, the IPBC content was still 2.09% by weight afterstorage for 11 months at room temperature, if3,3′-methylenebis(tetrahydro-2H-1,3-oxazine) was used as N-formal. TABLEXII Composition [% by wt.] C1 D C2 Mar 71 ™ 80 — 803,3′-Methylenebis(tetrahydro-2H-1,3-oxazine — 80 — IPBC 3 3 3 1,2-PLG 1717 17 — — — IPBC content zero value — — 2.92 IPBC content after 1 monthat RT — — 2.88 IPBC content after 3 months at RT 2.29 2.81 — IPBCcontent after 11 months at RT — 2.09 —

Example 9

[0094] Formaldehyde emission of N-formals

[0095] As well as characterizing their compatibility and stability withIPBC, the N-formals Mar 71™ and3,3′-methylenebis(tetrahydro-2H-1,3-oxazine) were tested with regard totheir formaldehyde emission behaviour and odour.

[0096] For this purpose, 1 g of each of the N-formals was left to standovernight in a 400 ml beaker covered with para-film. On the followingday, the formaldehyde content was then measured using Dräger tubes (10strokes) as described in Example 1.

[0097] The formaldehyde content was 15 ppm (2 strokes 3 ppm) in3,3′-methylenebis(tetrahydro-2H-1,3-oxazine) and 25 ppm (2 strokes 5ppm) in Mar 71™. Preparations of 80% by weight of each N-formal and 20%by weight of 1,2-propylene glycol display a clearly different behaviour.For example, the addition of 1,2-PLG to3,3′-methylenebis(tetrahydro-2H-1,3-oxazine) leads to a reduction in theformaldehyde content to form 1.5 to 2.5 ppm (20 strokes) and theaddition to Mar 71™ to a reduction to 10 ppm (5 strokes 5 ppm), theformaldehyde content being determined as described above for pureN-formals. The experiment shows that the addition of propylene glycolsignificantly reduces the formaldehyde emission of the N-formalsaccording to the invention.

We claim:
 1. Composition having broad effectiveness against bacteria andfungi, which comprises: (a) an iodopropynylbutyl compound selected fromthe group consisting of iodopropynylbutyl esters, ethers, acetals,carbamates and carbonates, and (b) a N-formal selected from the groupconsisting of 3,3′-methylene bis(5-methyloxazolidine), 3,3 ′-methylenebis(tetrahuydro-2H-1,3-oxazine) and1-aza-5-ethyl-3,7-dioxabicyclo(3,3,0)octane, or a combination thereof.2. Composition according to claim 1 , wherein the iodopropynylbutylcompound is iodopropynylbutyl carbamate (IPBC).
 3. Composition accordingto claim 1 , wherein the N-formal is 3,3′-methylenebis(5-methyloxazolidine).
 4. Composition according to claim 1 , whichalso includes one or more O-formal formed by the reaction of amonovalent or polyvalent, amino-substituted C1-C10 -alkyl, aryl, aralkylalcohol or of a glycol or glycolether and a formaldehyde-supplyingcompound.
 5. Composition according to claim 1 , wherein the O-formalsare selected from polyoxymethylene glycols, polyoxymethylene diacetatesand polyoxymethylene dimenthyl ethers.
 6. Composition according to claim1 , wherein the O-formal is formed by the reaction of 1,2-propyleneglycol, dipropylene glycol, ethylene glycol, butyl glycol, butyldiglycol or benzyl alcohol, and a formaldehyde-supplying compound. 7.Composition according to claim 1 , wherein the iodopropynylbutylcompound is iodopropynylbutyl carbamate and the formaldehyde donorcompound is 3,3′-methylenebis(5-methyloxazolidine).
 8. Compositionaccording to claim 1 , wherein the composition includes the followingcomponents: a) from 0.1 to 20% by weight of an iodopropynylbutylcompound; and b) from 99.9% to 80% by weight of N-formal.
 9. Compositionaccording to claim 8 , wherein the composition includes the followingcomponents: a) from 4 to 6% by weight of iodopropynylbutyl carbamate;and b) from 96 to 94% by weight of3,3′-methylenebis(5-methyloxazolidine).
 10. Composition according toclaim 1 , wherein the composition includes the following components: a)from 0.1 to 20% by weight of an iodopropynylbutyl compound; and b) from99.9 to 80% by weight of O-formal.
 11. Composition according to claim 10, wherein the composition includes the following components: a) from 4to 6% by weight of iodopropynylbutyl carbamate; and b) from 96 to 94% byweight of 1,2-propylene glycol hemiformal.
 12. Composition according toclaim 1 , wherein the composition includes the following components: a)from 0.1 to 20% by weight of an iodopropynylbutyl compound; and b) from99.9 to 80% by weight, preferably from 99 to 90% by weight of a mixtureof N- and O-formals, the weight ratio of N- to O-formals being from 10:1to 1:10.
 13. Composition according to claim 12 , wherein the compositionincludes the following components: a) from 4 to 6% by weight ofiodopropynylbutyl carbamate; and b) from 96 to 94% by weight of amixture of 3,3′-methylenebis(5-methyloxazolidine) and 1,2-propyleneglycol hemiformal.
 14. Composition according to claim 1 , wherein thecomposition is in stable liquid, viscous liquid or paste form. 15.Composition according to claim 1 , wherein the composition alsocomprises at least one of emission-reducing additives,viscosity-modifying additives, wetting agents, stabilizers and solvents.16. Composition according to claim 15 , wherein the solvents reduce theemission of formaldehyde or formaldehyde-containing substances. 17.Composition according to claim 16 , wherein the solvent is selected from1,2-propylene glycol, 1-methoxy-2-propanol, phenoxypropanol andphenoxyethanol.
 18. Composition according to claim 15 , wherein thecomposition includes the following components: a) from 0.1 to 20% byweight of an iodopropynylbutyl compound; and b) from 99.9 to 80% byweight of a mixture of N-formals and solvents or of a mixture ofO-formals and solvents or of a mixture of a combination of N- andO-formals and solvents, the weight ratio of formal to solvent being from50:1 to 1:10.
 19. Composition according to claim 18 , wherein thecomposition includes the following components: a) from 4 to 6% by weightof an iodopropynylbutyl compound; and b) from 96 to 94% by weight of amixture of N-formals and solvents or a mixture of O-formals and solventsor a mixture of a combination of N- and O-formals and solvents, theratio of formals to solvents being from 50:1 to 1:10.
 20. Compositionaccording to claim 1 , wherein the composition additionally comprisesfurther known biocidal active ingredients.
 21. Composition according toclaim 20 , wherein the additional biocidal active ingredient is anisothiazolone.
 22. Composition according to claim 20 , wherein theadditional biocidal active ingredient is N-octylisothiazolone or2-mercaptopyridine N-oxide.
 23. Composition according to claim 15 ,which comprises between 1% and 10% by weight of IPBC, between 85% and98.5% by weight of a stabilizer selected from triethanolamine,pyriondisulfide, sodium sulfate or aluminium oxide.
 24. Compositionaccording to claim 1 , wherein the composition is in the form of astable liquid concentrate, a stable working solution prepared bydiluting the concentrate, a stable suspension or a stable emulsion. 25.Method of increasing the stability and service life of industrialproducts containing industrial preservatives selected from the groupconsisting of container preservatives, fuel additives, cutting fluidpreservatives, preservatives which have been mixed with water, emulsionsand dispersions in the coatings industry or in metal working, householdproducts, and cosmetics, which comprises adding a biocidally effectiveamount of the composition of claim 1 to the industrial product as anactive agent.
 26. Industrial product which comprises as an active agent,a biocidally effective amount of the composition of claim 1 , saidindustrial product including industrial preservatives selected from thegroup consisting of container preservatives, fuel additives, cuttingfluid preservatives, preservatives which have been mixed with water,emulsions and dispersions in the coatings industry or in metal working,household products, and cosmetics.
 27. The industrial product accordingto claim 26 , wherein the composition is present from 1 to 10% byweight.
 28. The industrial product according to claim 27 , wherein thecomposition is present from 2 to 5% by weight.